CN116947086B - Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant - Google Patents
Pomegranate type Zn 2 SnO 4 Preparation method and application of nano flame retardant Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 35
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 241000219991 Lythraceae Species 0.000 title claims abstract description 23
- 235000014360 Punica granatum Nutrition 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- 239000004472 Lysine Substances 0.000 claims abstract description 10
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 11
- 239000011496 polyurethane foam Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000779 smoke Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000428 dust Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 30
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910007717 ZnSnO Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 241000508269 Psidium Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 241001083505 Punica Species 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
Pomegranate type Zn 2 SnO 4 A preparation method and application of nano particles belong to the technical field of nano composite materials and application thereof. The invention prepares the pomegranate type Zn with high dispersion, uniform grain diameter and stable structure for the first time by utilizing the guiding effect of lysine and polyacrylic acid 2 SnO 4 And (3) nanoparticles. Pomegranate-like Zn prepared by the invention 2 SnO 4 The nanoparticle has unique structure, and consists of a plurality of ultra-small Zn smaller than 10nm 2 SnO 4 Small particles. Ultrafine Zn 2 SnO 4 The secondary structure can rapidly catalyze the polymer to form carbon, a good flame-retardant carbon layer is formed, a pile-up pore canal of the flame-retardant carbon layer can adsorb harmful components in a large amount of smoke dust, harm of the smoke dust to human bodies is reduced while smoke is restrained, and excellent flame-retardant and smoke-restraining effects are shown.
Description
Technical Field
The invention belongs to the technical field of nano composite materials and application thereof, in particular to a pomegranate type Zn 2 SnO 4 A preparation method of nano particles and application thereof in flame retardant modification of polyurethane foam.
Background
Polyurethane is a high molecular polymer with a carbamate chain segment structure obtained by reacting isocyanate with polyol. Polyurethane foam has the advantages of good cohesiveness, chemical resistance, aging resistance and the like, and is widely applied to various production and living fields. However, polyurethane foam is extremely easy to burn and generates a large amount of smoke, so that the application of the polyurethane foam in the fields of aviation, transportation and the like is limited. Compared with the organic flame retardant, the inorganic flame retardant has the advantages of good heat stability, good smoke suppression effect, low cost, no toxicity, environmental protection and the like, and accords with the development trend of novel environmental-friendly flame retardants.
The Zn-O-Sn compound has good flame-retardant and smoke-suppressing effects, is nontoxic and has good thermal stability, and two important binary oxides exist in a Zn-O-Sn system: zn (zinc) 2 SnO 4 And ZnSnO 3 . Currently, for ZnSnO 3 Is a typical stannate of a faceted perovskite structure, and has a varied valence state and a special electronic structure. Because of the crystal structure, the gap between oxygen octahedrons is larger than that of the joint of the co-edge and the co-plane, the ion filling with larger size is allowed, the stability is maintained, the diffusion and migration of oxygen and defects are facilitated, and the ZnSnO is ensured 3 Has some special activity and structural characteristics. As a novel inorganic flame-retardant smoke suppressant, the flame-retardant smoke suppressant has the advantages of environmental protection, no toxicity and the like, is widely applied to the fields of high polymer materials such as PVC, polyester resin, alkyd resin, chlorinated rubber, epoxy resin, ethylene-ethyl acetate copolymer and the like, and is considered to be one of novel, stable, efficient and green flame retardants. Conventionally, as an environment-friendly flame retardant, the flame retardant has the characteristics of low addition amount, high flame retardant performance and the like, and can be used for replacing antimony trioxide (Sb 2 O 3 ) Is an environment-friendly product.
Although ZnSnO 3 Shows excellent environmental protection performance, but compared with the novel Zn 2 SnO 4 Exhibits better flame-retardant and smoke-eliminating performance [ chemical industry progress. 2019,38 (02), 933-939; china plastics 2013,27 (10), 52-57.]. But currently preparing nano-scale Zn 2 SnO 4 The material still has the defects of complex preparation process, high product cost, incapability of regulating and controlling the structure and the like, and the flame retardant effect is limited by the nano structure, the particle size and the dispersity, and how to controlThe nano structure, particle size distribution or surface modification is prepared, the flame retardant energy efficiency of the flame retardant is improved or the bonding capability with a base material is improved, and the nano structure, the particle size distribution or the surface modification becomes an important factor for promoting the market popularization of the tin-based flame retardant.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: provides a pomegranate type Zn 2 SnO 4 Preparation method and application of nano particles for solving the problem of preparing nano Zn at present 2 SnO 4 The material has the technical problems of complex preparation process, high product cost, incapability of regulating and controlling the structure and restriction on the flame retardant effect.
Pomegranate type Zn 2 SnO 4 A method of preparing nanoparticles comprising the steps of, and in sequence:
step one, proper deionized water, lysine, polyacrylic acid aqueous solution and NH are added 3 ·H 2 O and ethanol are slowly added into a round bottom flask in sequence, and after stirring for 10min to 20min, znNO is added 3 Adding the aqueous solution into the solution, and stirring and reacting for 4-5 hours to obtain a mixed solution;
step two, centrifugally separating the mixed solution obtained in the step one, taking the centrifugate, washing with water, then re-dispersing in the mixed solution of ethanol and water, ultrasonically dispersing for 5-8 min, and then sequentially adding a proper amount of NaOH aqueous solution and SnCl 4 Stirring the ethanol solution for 20-30 min to obtain a mixed solution II;
step three, the obtained mixed solution II is alternately centrifugally washed for three times by water and ethanol, the obtained solid is dried in an oven at 50-80 ℃ for 8-10 hours to obtain a solid substance, the solid substance is placed in a tubular furnace and calcined under the protection of argon, the temperature rising rate during calcination is 3-5 ℃/min, the temperature is 600-900 ℃ and the time is 3-5 hours, and the pomegranate type Zn is obtained 2 SnO 4 And (3) nanoparticles.
In the first step, deionized water is 30-50 mL; 60 mg-90 mg of lysine; the mass concentration of the polyacrylic acid aqueous solution is 0.3g/mL, and the dosage is 200 mu L-300 mu L; NH (NH) 3 ·H 2 O is 2M in molar concentration of 450. Mu.L to ultra-high600. Mu.L; the ethanol consumption is 80-100 mL; znNO 3 The molar concentration of the aqueous solution is 0.2M, and the dosage is 2 mL-3 mL.
The volume molar concentration of the NaOH aqueous solution is 4M, and the dosage is 400 mu L-600 mu L; the SnCl 4 The volume molar concentration of the ethanol solution is 0.1M, and the dosage is 2 mL-3 mL.
In the second step, the volume ratio of ethanol to water is 1:1 to 3:1, the dosage is 100 mL-150 mL.
And in the second step, the centrifugal speed is 6000 rpm-7000 rpm, and the centrifugal time is 5-7 min.
And in the third step, the centrifugal speed is 5000-7000 rpm, and the centrifugal time is 8-10 min.
Pomegranate type Zn prepared by the method 2 SnO 4 The application of the nano particles is applied to preparing flame-retardant polyurethane foam.
Through the design scheme, the invention has the following beneficial effects:
1. the invention prepares the pomegranate type Zn with high dispersion, uniform grain diameter and stable structure for the first time by utilizing the guiding effect of lysine and polyacrylic acid 2 SnO 4 And (3) nanoparticles.
2. Pomegranate-like Zn prepared by the invention 2 SnO 4 The nanoparticle has unique structure, and consists of a plurality of ultra-small Zn smaller than 10nm 2 SnO 4 Small particles. Ultrafine Zn 2 SnO 4 The secondary structure can rapidly catalyze the polymer to form carbon, a good flame-retardant carbon layer is formed, a pile-up pore canal of the flame-retardant carbon layer can adsorb harmful components in a large amount of smoke dust, harm of the smoke dust to human bodies is reduced while smoke is restrained, and excellent flame-retardant and smoke-restraining effects are shown.
Drawings
The invention is further described with reference to the drawings and detailed description which follow:
FIG. 1 shows a pomegranate type Zn prepared in accordance with the present invention 2 SnO 4 Scanning electron microscope pictures of the nano particles.
FIG. 2 shows a single guava type Zn prepared in accordance with the present invention 2 SnO 4 Scanning electron microscope image of nano particleAnd (3) a sheet.
FIG. 3 shows a punica granatum-like Zn prepared in accordance with the present invention 2 SnO 4 And (3) carrying out surface scanning electron microscope pictures on the nano particles.
FIG. 4 shows a punica granatum-like Zn prepared in accordance with the present invention 2 SnO 4 XRD spectrum of the nanoparticle.
Detailed Description
Step one, 30 mL-50 mL deionized water, 60 mg-90 mg lysine, 0.3g/mL polyacrylic acid 200 mu L-300 mu L, 2M NH 3 ·H 2 Sequentially and slowly adding 450-600 mu L of O and 80-100 mL of ethanol into a round-bottomed flask, stirring for 10-20 min, and then adding 0.2M ZnNO 3 Adding 2-3 mL of aqueous solution into the solution, and stirring and reacting for 4-5 h to obtain a mixed solution;
step two, centrifugally separating the mixed solution obtained in the step one, wherein the centrifugal speed is 6000 rpm-7000 rpm, the centrifugal time is 5-7 min, and taking the centrifugal material, washing the centrifugal material with water, and then re-dispersing the centrifugal material in 100-150 mL of mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:1 to 3:1, after ultrasonic dispersion for 5min to 8min, 400 to 600 mu L of 4M NaOH aqueous solution and 0.1M SnCl are added in sequence 4 2-3 mL of ethanol solution, and stirring for 20-30 min to obtain a mixed solution II;
and thirdly, alternately centrifuging and cleaning the obtained mixed solution II with water and ethanol for three times, wherein the centrifugal speed is 5000-7000 rpm, the centrifugal time is 8-10 min, and the solid matter obtained after the centrifugal matter is dried in an oven at 50-80 ℃ for 8-10 h is taken. Then placing the solid matter into a tube furnace, calcining under the protection of argon, wherein the temperature rising rate during calcining is 3 ℃/min-5 ℃/min, the temperature is 600 ℃ -900 ℃ and the time is 3 h-5 h, and obtaining the pomegranate type Zn 2 SnO 4 Nanoparticle, guava type Zn 2 SnO 4 Scanning electron microscope and XRD patterns of the nanoparticles are shown in figures 1 to 4.
Pomegranate type Zn prepared according to the method 2 SnO 4 The nanoparticles are used for preparing flame-retardant polyurethane foam.
Example 1:
sequentially adding 30mL of deionized water,60mg lysine, 200. Mu.L polyacrylic acid (0.3 g/mL), 450. Mu.L NH 3 ·H 2 O (2M) and 80mL of ethanol were slowly added to the round bottom flask in sequence. After stirring for 10min, 2mL ZnCl was added 2 (0.2M) aqueous solution was added to the above solution, and the reaction was stirred for 4 hours. After centrifugal separation (rotation speed: 6000rpm, time: 5 min), water washing, and ultrasonic dispersion from a newly dispersed mixed solution of 100mL ethanol and water (volume ratio of ethanol to water is 1:1) for 5min for later use. Another 400. Mu.L of aqueous NaOH (4M) and 2mL of SnCl were taken 4 Adding ethanol solution (0.1M) into the above solution, stirring for 20min, alternately centrifuging with water and ethanol for three times, centrifuging (rotation speed: 5000rpm, time: 8 min), and oven drying the centrifugate at 50deg.C for 8 hr. Then placing the solid in a tube furnace, calcining under the protection of argon, wherein the heating rate is 3 ℃/min, the temperature is 900 ℃ and the time is 3 hours, thus obtaining the pomegranate type Zn 2 SnO 4 And (3) nanoparticles.
Example 2:
sequentially 50mL deionized water, 80mg lysine, 300. Mu.L polyacrylic acid (0.3 g/mL), 600. Mu.L NH 3 ·H 2 O (2M) and 100mL of ethanol were slowly added to the round bottom flask in sequence. After stirring for 20min, 3mL ZnCl was added 2 (0.2M) aqueous solution was added to the above solution, and the reaction was stirred for 5 hours. After centrifugal separation (rotation speed: 7000rpm, time: 5 min), water washing, ultrasonic dispersion was carried out for 7min from a newly dispersed solution of 150mL of ethanol and water (volume ratio of ethanol to water: 2:1) for use. Another 600. Mu.L of aqueous NaOH (4M) and 3mL of SnCl were taken 4 Ethanol solution (0.1M) was added to the above solution, stirred for 30min, and then washed three times by alternate centrifugation with water and ethanol, and centrifuged (rotation speed: 7000rpm, time: 9 min), and the centrifuged was dried in an oven at 70℃for 10h. Then placing the solid in a tube furnace, calcining under the protection of argon, wherein the heating rate is 5 ℃/min, the temperature is 800 ℃ and the time is 4 hours, thus obtaining the pomegranate type Zn 2 SnO 4 And (3) nanoparticles.
Example 3:
sequentially adding 35mL deionized water, 90mg lysine, 300. Mu.L polyacrylic acid (0.3 g/mL), 500. Mu.L NH 3 ·H 2 O (2M) and 100mL of ethanol are slowly added to a round bottom in sequenceIn a flask. After stirring for 20min, 3mL ZnCl was added 2 (0.2M) aqueous solution was added to the above solution, and the reaction was stirred for 5 hours. After centrifugal separation (rotation speed: 6000rpm, time: 6 min), water washing, and ultrasonic dispersion from a newly dispersed mixed solution of 120mL of ethanol and water (volume ratio of ethanol to water is 3:1) for 5min for later use. Another 600. Mu.L of aqueous NaOH (4M) and 3mL of SnCl were taken 4 Adding ethanol solution (0.1M) into the above solution, stirring for 20min, alternately centrifuging with water and ethanol for three times, centrifuging (rotation speed: 6000rpm, time: 10 min), and oven drying the centrifugate at 60deg.C for 10 hr. Then placing the solid in a tube furnace, calcining under the protection of argon, wherein the heating rate is 5 ℃/min, the temperature is 700 ℃ and the time is 3 hours, thus obtaining the pomegranate type Zn 2 SnO 4 And (3) nanoparticles.
The pomegranate type Zn 2 SnO 4 The specific method for applying the nano particles to preparing the flame-retardant polyurethane foam comprises the following steps:
firstly, putting pomegranate type Zn 2 SnO 4 The nano particles are dissolved in water and are uniformly dispersed by ultrasound. Then the guava Zn is added according to different mass ratios 2 SnO 4 Adding the nanoparticle solution into reaction liquid of isocyanate (IPDI), catalyst and the like, stirring at a high speed, fully mixing, pouring the mixture which starts to foam into a mold, starting the foaming reaction in a room temperature environment, taking out the mold after the foam is cured, and standing for 3 hours in the room temperature environment to obtain the flame-retardant polyurethane foam.
Use of guava-type Zn with polyurethane foam without flame retardant as a control sample 2 SnO 4 Flame retardant performance test of flame retardant polyurethane foam prepared from nanoparticles:
LOI limiting oxygen index test-test is performed with reference to GB/T2406-1993, the sample size is 130mm by 6mm by mm; 10 specimens were tested for each group of samples and the results averaged.
UL94 vertical burn test: with reference to GB/T8627-1999 standard, the sample sizes were 25mm by 6mm; 10 specimens were tested for each group of samples and the results averaged.
The results of the LOI test on the polyurethane samples with different addition amounts are shown in Table 1.
TABLE 1 flame retardant Properties
Sample of | Additive amount/% | LOI/% |
Contrast sample | 0 | 20.5 |
1 | 3 | 25.2 |
2 | 5 | 26.3 |
3 | 10 | 27.6 |
4 | 15 | 28.3 |
5 | 20 | 29.0 |
As is clear from Table 1, as Zn 2 SnO 4 The LOI number of the added amount of the nano particles is increased from 20.5 percent to 29.0 percent,it can be seen that the flame-retardant nano particles have obvious synergistic effect on the flame retardance of polyurethane. The results of the vertical burning analysis of the flame retardant polyurethane are shown in table 2.
Table 2 vertical burn test data
As can be seen from Table 2, the pure polyurethane failed the combustion test, and the surface of the combustion result was hardly charred, indicating that the pure polyurethane was a inflammable substance. When a small amount of Zn is added into polyurethane 2 SnO 4 The nano particles can achieve obvious flame retardant effect, the UL94 grade of the sample is obviously improved, and an obvious carbon layer begins to appear on the surface of the combustion object.
Claims (5)
1. Pomegranate type Zn 2 SnO 4 The preparation method of the nano particles is characterized by comprising the following steps: comprising the following steps, and the following steps are carried out in sequence,
step one, proper deionized water, lysine, polyacrylic acid aqueous solution and NH are added 3 ·H 2 O and ethanol are slowly added into a round-bottom flask in sequence, and ZnNO is added after stirring for 10 min-20 min 3 Adding the aqueous solution into the solution, and stirring and reacting 4 h-5 h to obtain a mixed solution;
wherein, deionized water is 30 mL-50 mL; lysine 60 mg-90 mg; the mass concentration of the polyacrylic acid aqueous solution is 0.3g/mL, and the dosage is 200 mu L-300 mu L; NH (NH) 3 ·H 2 The molar concentration of O is 2M, and the dosage is 450-600 mu L; the ethanol consumption is 80 mL-100 mL; znNO 3 The volume molar concentration of the aqueous solution is 0.2-M, and the dosage is 2 mL-3 mL;
step two, centrifugally separating the mixed solution obtained in the step one, taking the centrifugate, washing with water, then re-dispersing in the mixed solution of ethanol and water, ultrasonically dispersing for 5-8 min, and then sequentially adding a proper amount of NaOH aqueous solution and SnCl 4 Stirring the ethanol solution for 20-30 min to obtain a mixed solution II;
said aqueous NaOH solutionThe volume molar concentration is 4M, and the dosage is 400 mu L-600 mu L; the SnCl 4 The volume molar concentration of the ethanol solution is 0.1M, and the dosage is 2 mL-3 mL;
step three, the obtained mixed solution II is alternately centrifugally washed three times by water and ethanol, the obtained solid is dried in an oven at 50-80 ℃ for 8 h-10 h to obtain a solid substance, the solid substance is placed in a tube furnace and calcined under the protection of argon, the temperature rising rate during calcination is 3-5 ℃/min, the temperature is 600-900 ℃ and the time is 3 h-5 h, and the pomegranate-type Zn is obtained 2 SnO 4 And (3) nanoparticles.
2. A pomegranate type Zn according to claim 1 2 SnO 4 The preparation method of the nano particles is characterized by comprising the following steps: in the second step, the volume ratio of ethanol to water is 1: 1-3: 1, the dosage is 100 mL-150 mL.
3. A pomegranate type Zn according to claim 1 2 SnO 4 The preparation method of the nano particles is characterized by comprising the following steps: and in the second step, the centrifugal speed is 6000 rpm-7000 rpm, and the centrifugal time is 5-7 min.
4. A pomegranate type Zn according to claim 1 2 SnO 4 The preparation method of the nano particles is characterized by comprising the following steps: and in the third step, the centrifugal speed is 5000-7000 rpm, and the centrifugal time is 8-10 min.
5. Pomegranate type Zn prepared by the method of claim 1 2 SnO 4 The application of the nano particles is characterized in that: the method is applied to preparing the flame-retardant polyurethane foam.
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